Highly active catalyst composition for polymerizing alpha-olefins

ABSTRACT

There is disclosed a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid support, containing magnesium, in a liquid medium with a transition metal compound, e.g., a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers. Also disclosed are methods of preparing polymers with the catalyst composition and the resulting polymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 444,152,filed on Nov. 24, 1982 and now U.S. Pat. No. 4,481,301, which is acontinuation-in-part of U.S. application Ser. No. 327,534, filed on Dec.4, 1981, the entire disclosures of both of which are incorporated hereinby reference.

BACKGROUND

The present invention relates to a method for polymerizingalpha-olefins, a catalyst for such a polymerization and a method forproducing such a catalyst. A particular aspect of the present inventionrelates to a method for producing linear low density polyethylene.

Linear low density polyethylene polymers possess properties whichdistinguish them from other polyethylene polymers such as homopolymersof polyethylene. Certain of these properties are described in theAnderson et al U.S. Pat. No. 4,076,698.

The Karol et al U.S. Pat. No. 4,302,566 describes a process forproducing certain linear low density polyethylene polymers in a gasphase, fluid bed reactor.

The Graff U.S. Pat. No. 4,173,547, Stevens et al U.S. Pat. No.3,787,384, Strobel et al U.S. Pat. No. 4,148,754 and the Ziegler,deceased et al U.S. Pat. No. 4,063,009 each describe variouspolymerization processes suitable for producing forms of polyethyleneother than linear low density polyethylene, per se.

The Graff U.S. Pat. No. 4,173,547 describes a supported catalystobtained by treating a support with both an organoaluminum compound andan organomagnesium compound followed by contacting this treated supportwith a tetravalent titanium compound.

The Stevens et al U.S. Pat. No. 3,787,384 and the Strobel et al U.S.Pat. No. 4,148,754 describe a catalyst prepared by first reacting asupport (e.g., silica containing reactive hydroxy groups) with anorganomagnesium compound (e.g., a Grignard reagent) and then combiningthis reacted support with a tetravalent titanium compound. According tothe teachings of both of these patents, no unreacted organomagnesiumcompound would seem to be present when the reacted support is contactedwith the tetravalent titanium compound.

The Ziegler, deceased et al U.S. Pat. No. 4,063,009 describes a catalystwhich is the reaction product of an organomagnesium compound (e.g., analkylmagnesium halide) with a tetravalent titanium compound. Thisreaction with the tetravalent titanium compound takes place in theabsence of a support material.

SUMMARY

The present invention relates to a process for preparing a supportedcatalyst composition for use in alpha-olefin polymerization reactions,said process comprising the steps of:

(i) contacting a solid, porous carrier having reactive OH groups with aliquid in the absence of ball milling, said liquid containing at leastone organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different and represent C₁ -C₁₂hydrocarbyl groups, provided that R' may also be halogen, and n is arational number from about 0.5 to 2, whereby organomagnesium is reactedwith OH groups on said carrier;

(ii) evaporating said liquid from step (i) to precipitate magnesium ontosaid carrier, said precipitated magnesium being selected from the groupconsisting of magnesium dihalide, unreacted organomagnesium and mixturesthereof, whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and

(iii) reacting said powder of step (ii) with at least one tetravalenttitanium compound in a liquid medium, the number of moles of saidtetravalent titanium compound being in excess of the number of OH groupson said carrier prior to reaction with said organomagnesium in step (i),said tetravalent titanium compound being soluble in said liquid medium,and said supported magnesium composition, including the supportedmaterial thereof, being essentially insoluble in said liquid medium,

whereby a reacted form of titanium which is insoluble in said liquidmedium becomes supported on said carrier.

The present invention also relates to a process for preparing asupported catalyst composition for use in alpha-olefin polymerizationreactions, said process comprising the steps of:

(i) contacting silica having from about 0.3 to about 0.7 moles/g of OHgroups with a liquid in the absence of ball milling, said liquidcontaining at least one organomagnesium composition having the empiricalformula

    RMgR'                                                      (II)

where R represents C₁ -C₁₂ hydrocarbyl group and R' represents halogen,at least a portion of said organomagnesium composition being soluble insaid liquid medium, the ratio of the number of moles of saidorganomagnesium composition to the number of moles of OH groups on saidsilica being from about 1.1 to about 2.5, whereby organomagnesium isreacted with OH groups on said silica,

(ii) evaporating said liquid from step (i) to precipitate magnesium ontosaid carrier, said precipitated magnesium being selected from the groupconsisting of magnesium dihalide, unreacted organomagnesium and mixturesthereof, whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and

(iii) reacting said powder of step (ii) with at least one tetravalenttitanium compound in a liquid medium, the number of moles of saidtetravalent titanium compound being in excess of the number of moles ofmagnesium supported on said silica, said tetravalent titanium compoundbeing soluble in said liquid medium, and said supported magnesiumcomposition, including the supported material thereof, being essentiallyinsoluble in said liquid medium,

whereby a reacted form of titanium which is insoluble in said liquidmedium becomes supported on said silica.

The present invention further relates to a process for preparing alinear low density polyethylene polymer having a density of 0.94 g/cc orless, said process comprising conducting the polymerization in thepresence of a catalyst prepared by a process comprising the steps of:

(i) contacting a solid, porous carrier having reactive OH groups with aliquid in the absence of ball milling, said liquid containing at leastone organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different and represent C₁ -C₁₂hydrocarbyl groups, provided that R' may also be halogen, and n is arational number from about 0.5 to 2, whereby organomagnesium is reactedwith OH groups on said carrier;

(ii) evaporating said liquid from step (i) to precipitate magnesium ontosaid carrier, said precipitated magnesium being selected from the groupconsisting of magnesium dihalide, unreacted organomagnesium and mixturesthereof, whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and

(iii) reacting said powder of step (ii) with at least one tetravalenttitanium compound in a liquid medium, the number of moles of saidtetravalent titanium compound being in excess of the number of OH groupson said carrier prior to reaction with said organomagnesium in step (i),said tetravalent titanium compound being soluble in said liquid medium,and said supported magnesium composition, including the supportedmaterial thereof, being essentially insoluble in said liquid medium,

whereby a reacted form of titanium which is insoluble in said liquidmedium becomes supported on said carrier.

The present invention further relates to a process for preparing alinear low density polyethylene polymer which is an ethylene/1-hexenecopolymer having a density of 0.93 g/cc or less, said process comprisingconducting the polymerization in a gas phase, fluid bed reactor in thepresence of a catalyst produced by a process comprising the steps of:

(i) contacting silica having from about 0.3 to about 0.7 moles/g of OHgroups with a liquid in the absence of ball milling, said liquidcontaining at least one organomagnesium composition having the empiricalformula

    RMgR'                                                      (II)

where R represents C₁ -C₁₂ hydrocarbyl group and R' represents halogen,at least a portion of said organomagnesium composition being soluble insaid liquid medium, the ratio of the number of moles of saidorganomagnesium composition to the number of moles of OH groups on saidsilica being from about 1.1 to about 2.5, whereby organomagnesium isreacted with OH groups on said silica,

(ii) evaporating said liquid from step (i) to precipitate magnesium ontosaid carrier, said precipitated magnesium being selected from the groupconsisting of magnesium dihalide, unreacted organomagnesium and mixturesthereof, whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and

(iii) reacting said powder of step (ii) with at least one tetravalenttitanium compound in a liquid medium, the number of moles of saidtetravalent titanium compound being in excess of the number of moles ofmagnesium supported on said silica, said tetravalent titanium compoundbeing soluble in said liquid medium, and said supported magnesiumcomposition, including the supported material thereof, being essentiallyinsoluble in said liquid medium,

whereby a reacted form of titanium which is insoluble in said liquidmedium becomes supported on said silica.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic illustration of a fluid bed process forproducing linear low density polyethylene (LLDPE).

FIG. 2 is a graph showing the variation in the density of LLDPE polymersaccording to the magnesium content of the polymerization catalyst of theinvention.

FIG. 3 is a graph showing the variation in density of LLDPE polymerswith the ratio of butene to ethylene in the feed using a prior artcatalyst and a catalyst according to the invention.

FIGS. 4 and 5 are graphs showing the variation in density of LLDPEpolymers with the ratio of hexene to ethylene in the feed using a priorart catalyst and catalysts according to the invention.

DETAILED DESCRIPTION

In accordance with an aspect of the present invention, supportedtitanium is incorporated onto a suitable support by impregnating thissupport with reactive magnesium and utilizing this supported reactivemagnesium to react with tetravalent titanium (i.e., titanium in the plus4 valence state) in a liquid medium. Unreacted titanium is soluble inthis liquid medium, while reacted titanium and supported reactivemagnesium are insoluble in this liquid medium.

As used herein, the concept of supporting a material on a carrier isintended to connote the incorporation of material (e.g., magnesiumcompositions and/or titantium compositions) onto the carrier by physicalor chemical means. Accordingly, supported material need not necessarilybe chemically bound to the carrier.

Catalysts produced according to aspects of the present invention may bedescribed in terms of the manner in which they can be made. Moreparticularly, these catalysts can be described in terms of the manner inwhich a suitable carrier may be treated in order to form such catalysts.

Suitable carrier materials which may be treated include solid, porouscarrier materials such as silica, alumina and combinations thereof. Suchcarrier materials may be amorphous or crystalline in form. Thesecarriers may be in the form of particles having a particle size of fromabout 0.1 micron to about 200 microns, more preferably from about 10 toabout 80 microns. Preferably, the carrier is in the form of sphericalparticles, e.g., spray dried silica. The internal porosity of thesecarriers may be larger than 0.2 cm³ /gm, e.g., larger than about 0.6 cm³/g. The specific surface area of these carriers may be larger than about50 m² /g, e.g., from about 150 to about 1500 m² /g.

It is desirable to remove physically bound water from the carriermaterial prior to contacting this material with water-reactive magnesiumcompounds. This water removal may be accomplished by heating the carriermaterial to a temperature from about 100° C. to an upper limit oftemperature represented by the temperature at which change of state orsintering occurs. A suitable range of temperatures may, thus, be fromabout 100° C. to about 800° C., e.g., from about 150° C. to about 250°C.

Chemically bound water, as represented by a presence of OH groups in thecarrier, may be present when the carrier is contacted withwater-reactive magnesium compounds in accordance with an aspect of thepresent invention. This chemically bound water may be present as about0.3 mmoles or more of OH groups per gram of carrier. Accordingly, anamount of, e.g., from about 0.5 to about 5 mmoles of OH groups per gramof carrier may be present, but a preferred range is from about 0.3 toabout 0.7 mmoles of OH groups per gram of carrier. Excess OH groupspresent in the carrier may be removed by heating the carrier for asufficient time at a sufficient temperature to accomplish the desiredremoval. More particularly, for example, a relatively small number of OHgroups may be removed by sufficient heating at from about 150° C. toabout 250° C., whereas a relatively large number of OH groups may beremoved by sufficient heating at at least 500° or 600° C., mostespecially, about from about 750° C. to about 850° C. The duration ofheating may be overnight, e.g., 16 hours or a shorter period, e.g., atleast 4 hours. The surface hydroxyl concentration of silica may bedetermined according to J. B. Peri and A. L. Hensley, Jr., J. Phys.Chem., 72 (8), 2926 (1968).

While heating is a preferred means of removing OH groups inherentlypresent in a carrier such as silica, other removal means are alsopossible such as chemical means. For example, a desired proportion of OHgroups may be reacted with a chemical agent such as a hydroxyl reactivealuminum compound, e.g., triethylaluminum.

Examples of suitable carrier materials are described in the Graff, U.S.Pat. No. 4,173,547. Note particularly the passage extending from column3, line 62 to column 5, line 44 of this Graff patent. It is noted thatinternal porosity of carriers can be determined by a technique termedBET-technique, described by S. Brunauer, P. Emmett and E. Teller inJournal of the American Chemical Society, 60, pp. 209-319 (1938).Specific surface areas of carriers can also be measured in accordancewith the above-mentioned BET-technique, with use of the standardizedmethod as described in British Standards BS 4359, Volume 1, (1969).

Further examples of carrier materials are given in the Stevens et al.,U.S. Pat. No. 3,718,636. Note particularly the passage extending fromline 12 to line 29 of column 3 of this Stevens et al patent. Alsoincluded as examples of carrier materials are polymeric silicas known aspolysiloxanes.

An example of a preferred carrier is silica which has been dehydrated byfluidizing with nitrogen and heating at about 800° C. for about 16 hoursto achieve a surface hydroxyl concentration of about 0.5 mmols/g. Thesilica used may be a high surface area, amorphous silica (surfacearea=300 m² /g; pore volume of 1.65 cm³ per gram) marketed under thetradename Davison 952 by the Davison Division of W. R. Grace and Co.

A suitable dehydrated carrier material may be further treated byimpregnating same with a solid magnesium containing composition which iscapable of reacting with a tetravalent titanium compound. One suchmagnesium containing material is an organomagnesium composition of theformula R_(n) MgR'.sub.(2-n), where R and R' are the same or differentand represent stable organic moieties, provided that R' may also behalogen, and n is a rational number from about 0.5 to 2. A particularexample of a solution of such an organomagnesium composition is aGrignard reagent.

Grignard reagents are described in Organic Chemistry, Second Edition,Morrison and Boyd, fifth printing, May 1968, pp. 112-114 and 516-521.Grignard reagents are known to react with organic molecules or moietieswhich have hydrogen bonded directly to a nitrogen or oxygen atom.Furthermore, Grignard reagents are also known to react with organicmolecules or moieties containing carbonyl groups, cyano groups and nitrogroups. Accordingly, stable organic moieties as defined by R in theabove-mentioned formula generally would not have any of theabove-mentioned groups indicated as being reactive with Grignardreagents. Thus, examples of R and R' include C₁ -C₁₂ hydrocarbyl groups(e.g., C₁ -C₁₂ alkyl or C₆ -C₁₂ aryl) or C₁ -C₁₂ alkoxy groups, whichmay be unsubstituted or substituted, e.g., with one or more of halogen(e.g., F, Cl, Br or I), C₁ -C₁₂ alkoxy, etc. A preferred compositionaccording to the formula R_(n) MgR'.sub.(2-n) is ethylmagnesiumchloride.

It is noted that even a Grignard reagent of ethylmagnesium chloride maycontain a mixture of molecules other than ethylmagnesium chloride, perse. For example, particularly under the influence of various liquids orsolvent systems, ethylmagnesium chloride may disproportionate to formessentially a mixture of magnesium dichloride and diethylmagnesium. Suchmixtures are intended to be encompassed within the formula R_(n)MgR'.sub.(2-n). Accordingly, it will be understood that compositions ofthe formula R_(n) MgR'.sub.(2-n) and compositions representative thereofare intended herein to represent the overall empirical formula of thesecompositions rather than to set forth the molecular formula of thesecompositions.

Preferably, the carrier should be impregnated such that the pores ofsame contain reactive solid magnesium containing composition. Apreferred means of accomplishing this result is by incorporating aporous carrier in a liquid medium containing a dissolved organomagnesiumcomposition of the formula R_(n) MgR'.sub.(2-n) and to cause magnesiumto become impregnated into the pores of the carrier by (1) a reaction ofthe organomagnesium composition with the carrier, by (2) a precipitationof magnesium from the organomagnesium composition onto the carrier or by(3) a combination of such reaction and precipitation.

Organo-magnesium compositions corresponding to those found in Grignardreagents have the formula RMgX, where R is as defined hereinabove and Xis halogen, (e.g., Cl, Br or I), and are soluble in ethers. Examples ofsuch ethers are mentioned on column 4, lines 32-49 of the Yamaguchi etal. U.S. Pat. No. 3,989,881 and include aliphatic ethers, such asdiethyl ether, diisopropyl ether, dibutyl ether, dipentyl ether andethyl-n-butyl ether; and cyclic ethers such as tetrahydrofuran anddioxane. It has been theorized that the reason for the ability of suchethers (e.g., diethyl ether) to solubilize such organomagnesiumcompositions (e.g., C₂ H₅ MgCl) is by virtue of the ability of themagnesium atom to act as a Lewis acid and to associate with at least oneelectron pair from the etheric oxygen which acts as a Lewis base. Suchan association is represented as follows: ##STR1##

Although organomagnesium compounds of the formula RMgX tend to beinsoluble in non-Lewis base solvents such as hexane, theseorganomagnesium compounds may be completely soluble in mixed solventsystems such as hexane/tetrahydrofuran, provided that a sufficientsolubilizing amount of the Lewis base solvent is present. Thus,according to one aspect of the present invention, a carrier may beslurried in a non-Lewis base co-solvent and an organomagnesium compoundmay be added thereto in the form of an ether solution thereof. Examplesof non-Lewis base co-solvents are given in the passage extending fromcolumn 6, line 61 to column 7, line 8 of the Graff U.S. Pat. No.4,173,547. These co-solvents include straight or branched saturatedaliphatic hydrocarbons, such as butanes, pentanes, hexanes, heptanes, orcommonly available mixtures thereof, generally known as gasoline,kerosene, gas, oil or other petroleum fractions. Further, suchco-solvents include cyclic hydrocarbons, such as cyclopentane,cyclohexane, methylcyclohexane, as well as aromatic hydrocarbons, suchas benzene or halogen-aromatic hydrocarbons such as chlorobenzene. It isnoted that such co-solvents should preferably not contain groups whichare reactive with the organomagnesium composition. A preferredco-solvent is n-hexane.

According to another aspect of the present invention, carrier isimpregnated with magnesium composition by suitably contacting thiscarrier with a liquid containing organomagnesium composition of theformula R_(n) MgR'.sub.(2-n) in a partially dissolved state. Moreparticularly, the carrier may be slurried in one of theabove-exemplified non-Lewis base co-solvents, such as hexane, and asolution of Grignard in ether may be added thereto, the amount of etherrelative to the amount of co-solvent being sufficient to only partiallysolubilize the Grignard. The non-soluble portion of the Grignard may bein the form of dihalomagnesium, the amount of this non-solubledihalomagnesium being essentially equivalent to an amount ofdialkylmagnesium remaining soluble in the solvent/co-solvent mixture.

It is noted that if the organomagnesium compound is only sparinglysoluble, e.g., to the extent of even 1 percent or less, reactiveorganomagnesium which is consumed by reactive sites on the carrier willbe replaced by further dissolution of undissolved organomagnesium by amass action effect.

Another example of a means of impregnating is to slurry the carrier in aLewis base solvent such as an ether and to add a solution oforganomagnesium in ether to this slurry, the addition oforganomagnesium/ether solution to ether or co-solvent/carrier slurry maytake place as a gradual continuous dropwise addition while the liquidmedium of the slurry is maintained under reflux conditions. Upon suchaddition, dissolved organomagnesium composition may react with thecarrier at the site of reactive OH groups, if any, appearing on theavailable surface area of the carrier. Such a reaction may bedemonstrated with respect to ethylmagnesium chloride as follows:

    CARRIER--OH+C.sub.2 H.sub.5 MgCl→CARRIER--OMgCl+C.sub.2 H.sub.6 ↑

Accordingly, it may be possible to incorporate a magnesium compositiononto a carrier by reacting an organomagnesium composition with reactiveOH groups of the carrier.

Another means of incorporating a magnesium composition onto a carrier isto precipitate magnesium from an organomagnesium composition from aliquid onto a carrier. This precipitation may take place by any possibleconvenient means including cooling of the solvent, using a sufficientlylarge amount of non-solvent in the initial slurry, adding non-solvent tothe slurry or stripping off solvent. In the case of a carrier slurrywhere the liquid medium is essentially a hexane/tetrahydrofuran solutionof ethylmagnesium chloride, it is preferred to precipitateethylmagnesium chloride onto the carrier by distillation of the solvent.In this regard, it is noted that tetrahydrofuran and hexane have nearlyequivalent boiling points. Thus, it would be expected that during thecourse of distilling these solvents, the ratio of tetrahydrofuran tohexane in the liquid state would remain essentially constant. On theother hand, if the boiling point of the co-solvent is significantlygreater than the boiling point of the ether, then the relativeconcentration of co-solvent may increase appreciably as the distillationproceeds. In such a case, a non-uniform precipitation of magnesium mayoccur, such that any magnesium dihalide which is present tends toprecipitate before organomagnesium is precipitated.

Particularly in view of the above discussion, it will be understood thatat least three possible types of supported magnesium compositions can beobtained. The first type is essentially a reaction product of anorganomagnesium composition with a carrier having OH functionalitieswhich are reactive with this organomagnesium composition. This productwould contain essentially no precipitated organomagnesium composition.Examples of such reaction products are given in the aforementionedStevens et al U.S. Pat. No. 3,787,384 and Strobel et al U.S. Pat. No.4,148,754.

A second type of product is essentially an organomagnesium compositionsupported on a carrier. This product would contain essentially noreaction product of organomagnesium with the carrier. Such a productcould result when an organomagnesium composition is precipitated onto acarrier having essentially no OH functionalities reactive with theorganomagnesium composition.

A third type of product contains both reacted organomagnesiumcomposition and precipitated organomagnesium composition. Such a productcould result when an excess of organomagnesium is precipitated in thepresence of a carrier containing reactive OH functionalities.

Accordingly, magnesium may be incorporated onto a carrier in either anunreacted form or in a reacted form, this reaction taking place betweenreactive hydroxyl groups of the carrier and an organomagnesiumcomposition. The molar ratio of organomagnesium composition used toimpregnate the carrier with respect to the hydroxyl groups of thecarrier may be, e.g., from about 0.5 to about 3. When an excess oforganomagnesium is used, this ratio may be, e.g., from about 1.1 toabout 2.5.

Whether magnesium is in the form of a reaction product with the carrieror in the form of a non-reacted precipitate, it is noted that thissupported magnesium may, optionally, be in the form of a complex withone or more electron donating agents (i.e. Lewis bases). Moreparticularly, when ethylmagnesium chloride is precipitated from ahexane/tetrahydrofuran solution, each mole of ethylmagnesium chlorideprecipitated may be complexed with approximately one mole oftetrahydrofuran. In more general terms, when an organomagnesiumcomposition is precipitated from a solution containing an ether, theresulting precipitate may have molecules of this ether complexed withmolecules of the organomagnesium composition.

The amount of magnesium composition which is impregnated onto thecarrier should be sufficient to react with tetravalent titanium in orderto incorporate a catalytically effective amount of titanium on thecarrier in the manner set forth hereinbelow. More particularly, forexample, from about 0.1 to about 5 or even 50 mmoles of magnesium may beimpregnated per gram of carrier initially present. When a liquidcontaining an organomagnesium composition is contacted with a carrierthe amount of magnesium in this liquid in terms of mmoles may beessentially the same as that stated above with respect to that which isimpregnated onto the carrier.

When a non-Lewis base co-solvent is used to slurry the carrier, anamount of such co-solvent sufficient to slurry such carrier may be used.More particularly, for example, from about 2 to about 100 mls of suchco-solvent may be present per gram of carrier. A preferred narrowerrange would be from about 5 to about 15 mls of co-solvent per gram ofcarrier.

The amount and concentration of organomagnesium/ether solution which isadded to the co-solvent/carrier slurry are preferably sufficient toassure that the organomagnesium composition is at least partiallysoluble in the co-solvent/solvent system. Thus, this amount is dependentupon many factors such as the composition of solvents andorganomagnesium, the temperature of the co-solvent/solvent system, etc.However, it will be readily understood that the selection of properamounts and concentrations of organomagnesium/ether solutions is wellwithin the ability of those of ordinary skill in the art. Moreparticularly, for example, when an ethylmagnesiumchloride/tetrahydrofuran solution is added to a hexane/carrier slurry,the concentration of the ethylmagnesium chloride/tetrahydrofuransolution may be from about 0.1 to about 10 Molar. A preferred narrowerrange would be from about 1 to about 3 Molar.

For example, when 107 g of silicic acid are suspended in 500 ml ofn-heptane and 342 ml of a solution of 172 mmols of n-propyl magnesiumchloride in diethyl ether are added thereto in accordance with Example 1of the Strobel et al U.S. Pat. No. 4,148,754, the n-propyl magnesiumchloride may well be totally soluble in the n-heptane/diethyl ethermixture. However, when 15 g of silica are slurried in 200 ml of n-hexaneand 50 ml of a 2.0 molar solution of ethylmagnesium chloride intetrahydrofuran is added thereto in accordance with Example 1 givenherein, infra, the ethylmagnesium chloride appears to be only partiallysoluble in the n-hexane/tetrahydrofuran mixture.

While the above-exemplified methods of incorporating a solid reactivemagnesium composition onto a carrier are preferred, it will beunderstood that alternative methods are available. For instance, it ispossible to precipitate a dialkylmagnesium composition onto a carrierfrom a hydrocarbyl or halohydrocarbyl solvent containing essentially noether. It is also possible to combine carrier and a solidorganomagnesium composition in the absence of a solvent by means of aball milling device. However, such a ball milling process is lesspreferred, particularly because it does not tend to effectivelyincorporate a reactive magnesium compound into the pores of the carrier.

It is particularly noted that mechanical shearing means such as ballmilling are not necessary to achieve the desired impregnation ofcatalyst onto carrier in accordance with aspects of the presentinvention. Accordingly, a ball milling process such as described inExamples 2-5 of the Grant U.S. Pat. No. 3,821,186 is unnecessary and maybe avoided. Moreover, a ball milling process may tend to disrupt theparticle size and morphology of the carrier. Since catalysts made inaccordance with aspects of the present invention are preferably capableof being used in gas phase, fluid bed polymerizations, e.g., asdescribed in the Karol et al U.S. Pat. No. 4,302,566, the particle sizeand morphology of the catalyst may be rather critical. Accordingly,another reason for avoiding ball milling is to preserve the particlesize and morphology of the carrier while it is being treated inaccordance with aspects of the present invention.

The solid supported magnesium-containing composition is preferably inthe form of a free-flowing powder when dry. It is particularly notedthat when a carrier is impregnated by many of the above-exemplifiedmethods neither the carrier nor the magnesium is contacted with eitheran organoaluminum compound or an aluminum halide compound. Thus, such atreatment with a significant amount of an organoaluminum compound or analuminum halide compound is preferably not part of the presentinvention.

A carrier treated with an organomagnesium composition according to theabove-exemplified methods may be reacted with a tetravalent titaniumcompound in a liquid medium. The tetravalent titanium compound issoluble in this liquid reaction medium, while the treated carrier,including the magnesium containing portion thereof, is insoluble in thisliquid reaction medium. Thus, the reaction which takes place between thetetravalent titanium and the reactive magnesium-containing compositionis a reaction of a solid with a liquid. It is further noted that thereacted titanium is insoluble in the liquid reaction medium.

The reaction which takes place between a solid, supportedorganomagnesium compound and tetravalent titanium in the liquid reactionmedium is felt to be essentially an oxidation/reduction reaction,wherein the organomagnesium composition acts as a reducing agent for thetetravalent titanium. On the other hand, while not wishing to be boundby any particular theory or chemical mechanism, the reaction which takesplace between (1) tetravalent titanium and (2) the reaction product of aGrignard reagent and carrier containing reactive OH groups is not feltto be an oxidation/reduction reaction. However, it is noted that both ofthe above-mentioned reactions lead to the incorporation of titanium ontoa support corresponding to the treated carrier.

Examples of tetravalent titanium compounds, which may be used in theliquid reaction medium, are given in the passage extending from line 35to line 54 of column 6 of the Graff U.S. Pat. No. 4,173,547. Suchexamples include titanium halides (e.g., where the halide portionthereof is Cl or Br), titanium alkoxides (e.g., where the alkoxideportion thereof is a C₁ -C₆ alkoxide), or mixtures thereof. A preferredtetravalent titanium compound is TiCl₄.

It may also be possible to replace some or all of the above-mentionedtetravalent titanium compounds with one or more other transition metalcompounds. Such other transition metal compounds are exemplified in thepassage extending from line 55 to line 60 of column 6 of the Graff et alU.S. Pat. No. 4,173,547. Preferred transition metal compounds includezirconium compounds (e.g., ZrCl₄) and, especially, vanadium compounds(e.g., VCl₃).

The liquid portion of the liquid reaction medium is preferably asolution of the tetravalent titanium compound in a solvent which may beone or more of the organic liquids exemplified hereinabove as beingsuitable for use as a co-solvent in the impregnation of the carrier withreactive magnesium composition. A preferred solvent for the tetravalenttitanium compound is n-heptane.

The reaction of the tetravalent titanium compound in the liquid mediumconveniently takes place by slurrying the solid carrier containing thereactive magnesium composition in a solution of the tetravalent titaniumcompound and heating the liquid reaction medium to a suitable reactiontemperature, e.g., to the reflux temperature of the solvent at standardatmospheric pressure. Thus, the reaction may take place under refluxconditions.

The various reaction parameters are subject to a wide variety ofpossibilities, suitable selection of such parameters being well withinthe skill of those having ordinary skill in the art. However, forexample, the volume of tetravalent titanium solution to treated carrierinitially slurried in the solution may be from about 0.1 to about 10 mlsper gram of such carrier. The concentration of the tetravalent titaniumsolution may be, for example, from about 0.1 to about 5 Molar. Theamount of tetravalent titanium in solution may be, e.g., in excess ofthe molar amount of organomagnesium earlier used to treat the carrier.More particularly, for example, the molar ratio of tetravalent titaniumto organomagnesium may be from about 1 to about 10, more particularlyfrom about 3 to about 6. These ratios given for tetravalent titanium toorganomagnesium are generally representative of acceptable ratios fortetravalent titanium to measurable hydroxyl groups on the carrier.Unreacted titanium may be removed by suitable separation techniques suchas decantation, filtration and washing.

The supported catalyst may be activated with suitable activators. Suchsuitable activators include those organometallic compounds described inthe passage extending from column 4, line 45 to column 5, line 12 of theStevens et al U.S. Pat. No. 3,787,384 and in the passage extending fromcolumn 4, line 56 to column 5, line 59 of the Strobel et al U.S. Pat.No. 4,148,754. A preferred activator is triethylaluminum.

The catalyst may be activated in situ by adding the activator andcatalyst separately to the polymerization medium. It is also possible tocombine the catalyst and activator before introduction into thepolymerization medium, e.g., for up to about 2 hours at a temperaturefrom about -40° to about 80° C. Still other types of combinations ofcatalysts and activators are possible (note the passage extending fromline 50 to line 60 in column 5 of the Stevens et al U.S. Pat. No.3,787,384).

A suitable activating amount of the activator may be used. The number ofmoles of activator per gram atom of titanium in the catalyst may be,e.g., from about 1 to about 100 and is preferably greater than about 5(note the passage extending from column 5, line 71 to column 6, line 2of the Stevens et al U.S. Pat. No. 3,787,384).

Alpha-olefins may be polymerized with the catalysts prepared accordingto aspects of the present invention by any suitable process. Suchprocesses include polymerizations carried out in suspension, in solutionor in the gas phase (note the passage extending from line 25 to line 31in column 6 of the Strobel et al U.S. Pat. No. 4,148,754 and the passageextending from line 32 to line 49 in column 5 of the Stevens et al U.S.Pat. No. 3,787,384). Gas phase polymerizations are preferred such asthose taking place in stirred bed reactors and, especially, fluidizedbed reactors.

The molecular weight of the polymer may be controlled in a known manner,preferably by using hydrogen. With the catalysts produced according toaspects of the present invention, molecular weight may be suitablycontrolled with hydrogen when the polymerization is carried out atrelatively low temperatures, e.g., from about 30° to about 105° C. Thiscontrol of molecular weight may be evidenced by a measurable positivemelt index for the polymer produced.

The catalysts prepared according to aspects of the present invention arehighly active and may have an activity of at least about 5.8, e.g., fromabout 5.8 to about 11.6 in terms of grams of polymer produced per hourper mmole of Ti per kPa of ethylene pressure.

The catalysts prepared according to aspects of the present invention areparticularly useful for the production of linear low densitypolyethylene polymers. Such linear low density polyethylene polymers mayhave a density of 0.94 g/cc or less, preferably 0.930 or less or even0.925 g/cc or less. In accordance with certain aspects of the presentinvention, it is possible to achieve densities of less than 0.915 g/ccand even 0.900 g/cc or less.

Advantageous properties of linear low density polyethylene polymers aredescribed in the Anderson et al U.S. Pat. No. 4,076,698. These linearlow density polyethylene polymers may be polymers of ethylene with oneor more C₃ -C₁₀ alpha-olefins. Thus, copolymers having two monomericunits are possible as well as terpolymers having three monomeric units.Particular examples of such polymers include ethylene/1-butenecopolymers, ethylene/1-hexene copolymers, ethylene/4-methyl-1-pentenecopolymers, ethylene/1-butene/1-hexene terpolymers,ethylene/propylene/1-hexene terpolymers and ethylene/propylene/1-buteneterpolymers. When propylene is employed as a comonomer, the resultinglinear low density polyethylene polymer preferably has at least oneother alpha-olefin comonomer having at least four carbon atoms in anamount of, e.g., at least 1 percent by weight of the polymer.Accordingly, ethylene/propylene copolymers are possible, but notpreferred.

The linear low density polyethylene polymers produced in accordance withcertain aspects of the present invention preferably contain at leastabout 80 percent by weight of ethylene units.

A particularly desirable method for producing linear low densitypolyethylene polymers, according to an aspect of the present invention,is felt to be via a fluid bed reactor. Such a reactor and means foroperating same is described in the Levine et al U.S. Pat. No. 4,011,382or the Karol et al U.S. Pat. No. 4,302,566. The activity of the catalystproduced in accordance with certain aspects of the present invention isfelt to be sufficient to produce a linear low density polyethylenepolymer which is an ethylene/1-hexene copolymer, e.g., having a densityof less than 0.930 g/cc, in such a fluid bed reactor.

As described in the Karol et al U.S. Pat. No. 4,302,566, a preferredprocess for conducting a gas phase, fluid bed polymerization is asfollows.

The polymerization reaction is conducted by contacting a stream of themonomers, in a gas phase process, such as in the fluid bed processdescribed below, and substantially in the absence of catalyst poisonssuch as moisture, oxygen, CO, CO₂, and acetylene with a catalyticallyeffective amount of the completely activated catalyst at a temperatureand at a pressure sufficient to initiate the polymerization reaction.

In order to achieve the desired density ranges in the copolymers it isnecessary to copolymerize enough of the ≧C₃ comonomers with ethylene toachieve a level of >0 to 10 mol percent of the C₃ to C₈ comonomer in thecopolymer. The amount of comonomer needed to achieve this result willdepend on the particular comonomer(s) employed.

In accordance with the invention, it has unexpectedly been found thatusing a gas phase catalytic polymerization reaction, 1-hexene (e.g.normal 1-hexene, and/or 4-methyl-1-pentene) can be incorporated into anethylene polymer chain with high efficiency. In other words, arelatively small concentration of 1-hexene monomer in the gas phasereactor can lead to a relatively large incorporation of 1-hexene intothe polymer. Thus, 1-hexene can be incorporated into an ethylene polymerchain in a gas phase reactor in amounts up to 20 percent by weight,preferably 5 to 11 percent by weight, to produce linear low densitypolyethylene having a density of less than 0.930 g/cc. The reaction ispreferably conducted in a fluid bed reactor using the catalyst accordingto the invention prepared by impregnating a carrier with both reactedand precipitated magnesium being in excess of the number of moles of OHgroups in the carrier, and then reacting this impregnated carrier with atitanium compound in molar excess with respect to supported magnesium.This preferred process is most useful when polymers having a density of0.920 g/cc are required. However, when higher densities are desired, itis possible to employ catalysts in which the only magnesium present isreacted with the carrier (i.e. in the substantial absence ofprecipitated magnesium) and/or where the titanium compound is reactedwith the supported magnesium composition in a molar ratio of one or lesswith the magnesium.

A fluidized bed reaction system which can be used in the practice of theprocess of the present invention is illustrated in FIG. 1. Withreference thereto the reactor 10 consists of a reaction zone 12 and avelocity reduction zone 14.

The reaction zone 12 comprises a bed of growing polymer particles,formed polymer particles and a minor amount of catalyst particlesfluidized by the continuous flow of polymerizable and modifying gaseouscomponents in the form of make-up feed and recycle gas through thereaction zone. To maintain a viable fluidized bed, the mass gas flowrate through the bed must be above the minimum flow required forfluidization, and preferably from about 1.5 to about 10 times G_(mf) andmore preferably from about 3 to about 6 times G_(mf).G_(mf) is used inthe accepted form as the abbreviation for the minimum mass gas flowrequired to achieve fluidization, C. Y. Wen and Y. H. Yu, "Mechanics ofFluidization", Chemical Engineering Progress Symposium Series, Vol. 62,p. 100-111 (1966).

It is essential that the bed always contains particles to prevent theformation of localized "hot spots" and to entrap and distribute theparticulate catalyst throughout the reaction zone. On start up, thereaction zone is usually charged with a base of particulate polymerparticles before gas flow is initiated. Such particles may be identicalin nature to the polymer to be formed or different therefrom. Whendifferent, they are withdrawn with the desired formed polymer particlesas the first product. Eventually, a fluidized bed of the desired polymerparticles supplants the start-up bed.

The partially or completely activated catalyst used in the fluidized bedis preferably stored for service in a reservoir 32 under a blanket of agas which is inert to the stored material, such as nitrogen or argon.

Fluidization is achieved by a high rate of gas recycle to and throughthe bed, typically in the order of about 50 times the rate of feed ofmake-up gas. The fluidized bed has the general appearance of a densemass of viable particles in possible free-vortex flow as created by thepercolation of gas through the bed. The pressure drop through the bed isequal to or slightly greater than the mass of the bed divided by thecross-sectional area. It is thus dependent on the geometry of thereactor.

Make-up gas is fed to the bed at a rate equal to the rate at whichparticulate polymer product is withdrawn. The composition of the make-upgas is determined by a gas analyzer 16 positioned above the bed. The gasanalyzer determines the composition of the gas being recycled and thecomposition of the make-up gas is adjusted accordingly to maintain anessentially steady state gaseous composition within the reaction zone.

To insure complete fluidization, the recycle gas and, where desired,part of the make-up gas are returned to the reactor at point 18 belowthe bed. There exists a gas distribution plate 20 above the point ofreturn to aid fluidizing in the bed.

The portion of the gas stream which does not react in the bedconstitutes the recycle gas which is removed from the polymerizationzone, preferably by passing it into a velocity reduction zone 14 abovethe bed where entrained particles are given an opportunity to drop backinto the bed. Particle return may be aided by a cyclone 22 which may bepart of the velocity reduction zone or exterior thereto. Where desired,the recycle gas may then be passed through a filter 24 designed toremove small particles at high gas flow rates to prevent dust fromcontacting heat transfer surfaces and compressor blades.

The recycle gas is then compressed in a compressor 25 and then passedthrough a heat exchanger 26 wherein it is stripped of heat of reactionbefore it is returned to the bed. By constantly removing heat ofreaction, no noticeable temperature gradient appears to exist within theupper portion of the bed. A temperature gradient will exist in thebottom of the bed in a layer of about 6 to 12 inches, between thetemperature of the inlet gas and the temperature of the remainder of thebed. Thus, it has been observed that the bed acts to almost immediatelyadjust the temperature of the recycle gas above this bottom layer of thebed zone to make it conform to the temperature of the remainder of thebed thereby maintaining itself at an essentially constant temperatureunder steady state conditions. The recycle is then returned to thereactor at its base 18 and to the fluidized bed through distributionplate 20. The compressor 25 can also be placed upstream of the heatexchanger 26.

The distribution plate 20 plays an important role in the operation ofthe reactor. The fluidized bed contains growing and formed particulatepolymer particles as well as catalyst particles. As the polymerparticles are hot and possibly active, they must be prevented fromsettling, for if a quiescent mass is allowed to exist, any activecatalyst contained therein may continue to react and cause fusion.Diffusing recycle gas through the bed at a rate sufficient to maintainfluidization at the base of the bed is, therefore, important. Thedistribution plate 20 serves this purpose and may be a screen, slottedplate, perforated plate, a plate of the bubble cap type, and the like.The elements of the plate may all be stationary, or the plate may be ofthe mobile type disclosed in U.S. Pat. No. 3,298,792. Whatever itsdesign, it must diffuse the recycle gas through the particles at thebase of the bed to keep them in a fluidized condition, and also serve tosupport a quiescent bed of resin particles when the reactor is not inoperation. The mobile elements of the plate may be used to dislodge anypolymer particles entrapped in or on the plate.

Hydrogen may be used as a chain transfer agent in the polymerizationreaction of the present invention. The ratio of hydrogen/ethyleneemployed will vary between about 0 to about 2.0 moles of hydrogen permole of the monomer in the gas stream.

Any gas inert to the catalyst and reactants can also be present in thegas stream. The activator compound is preferably added to the reactionsystem at the hottest portion of the gas which is usually downstreamfrom heat exchanger 26. Thus, the activator may be fed into the gasrecycle system from dispenser 27 through line 27A.

Compounds of the structure Zn(R_(a))(R_(b)), wherein R_(a) and R_(b) arethe same or different C₁ to C₁₄ aliphatic or aromatic hydrocarbonradicals, may be used in conjunction with hydrogen, with the catalystsof the present invention as molecular weight control or chain transferagents, that is, to increase the melt index values of the copolymersthat are produced. About 0 to 50, and preferably about 20 to 30, mols ofthe Zn compound (as Zn) would be used in the gas stream in the reactorper mol of titanium compound (as Ti) in the reactor. The zinc compoundwould be introduced into the reactor preferably in the form of a dilutesolution (2 to 30 weight percent) in hydrocarbon solvent or absorbed ona solid diluent material, such as silica, of the types described above,in amounts of about 10 to 50 weight percent. These compositions tend tobe pyrophoric. The zinc compound maybe added alone, or with anyadditional portions of the activator compound that are to be added tothe reactor from a feeder, not shown, which could be positioned adjacentdispenser 27, near the hottest portion of the gas recycle system.

It is essential to operate the fluid bed reactor at a temperature belowthe sintering temperature of the polymer particles. To insure thatsintering will not occur, operating temperatures below the sinteringtemperature are desired. For the production of ethylene copolymers inthe process of the present invention an operating temperature of about30° to 115° C. is preferred, and a temperature of about 75° to 95° C. ismost preferred. Temperatures of about 75° to 90° C. are used to prepareproducts having a density of about 0.91 to 0.92, and temperatures ofabout 80° to 100° C. are used to prepare products having a density ofabout >0.92 to 0.94, and temperatures of about 90° to 115° C. are usedto prepare products having a density of about >0.94 to 0.96.

The fluid bed reactor is operated at pressures of up to about 1000 psi,and is preferably operated at a pressure of from about 150 to 350 psi,with operation at the higher pressures in such ranges favoring heattransfer since an increase in pressure increases the unit volume heatcapacity of the gas.

The partially or completely activated catalyst is injected into the bedat a rate equal to its consumption at a point 30 which is above thedistribution plate 20. Injecting the catalyst at a point above thedistribution plate is an important feature of this invention. Since thecatalysts used in the practice of this invention are highly active,injection of the fully activated catalyst into the area below thedistribution plate may cause polymerization to begin there andeventually cause plugging of the distribution plate. Injection into theviable bed, instead, aids in distributing the catalyst throughout thebed and tends to preclude the formation of localized spots of highcatalyst concentration which may result in the formation of "hot spots".

A gas which is inert to the catalyst such as nitrogen or argon is usedto carry the partially or completely reduced precursor composition, andany additional activator compound or non-gaseous chain transfer agentthat is needed, into the bed.

The production rate of the bed is controlled by the rate of catalystinjection. The production rate may be increased by simply increasing therate of catalyst injection and decreased by reducing the rate ofcatalyst injection.

Since any change in the rate of catalyst injection will change the rateof generation of the heat of reaction, the temperature of the recyclegas is adjusted upwards or downwards to accommodate the change in rateof heat generation. This insures the maintenance of an essentiallyconstant temperature in the bed. Complete instrumentation of both thefluidized bed and the recycle gas cooling system is, of course,necessary to detect any temperature change in the bed so as to enablethe operator to make a suitable adjustment in the temperature of therecycle gas.

Under a given set of operating conditions, the fluidized bed ismaintained at essentially a constant height by withdrawing a portion ofthe bed as product at a rate equal to the rate of formation of theparticulate polymer product. Since the rate of heat generation isdirectly related to product formation, a measurement of the temperaturerise of the gas across the reactor (the difference between inlet gastemperature and exit gas temperature) is determinative of the rate ofparticulate polymer formation at a constant gas velocity.

The particulate polymer product is preferably continuously withdrawn ata point 34 at or close to the distribution plate 20 and in suspensionwith a portion of the gas stream which is vented before the particulatessettle to preclude further polymerization and sintering when theparticles reach their ultimate collection zone. The suspending gas mayalso be used, as mentioned above, to drive the product of one reactor toanother reactor.

The particulate polymer product is conveniently and preferably withdrawnthrough the sequential operation of a pair of timed valves 36 and 38defining a segregation zone 40. While valve 38 is closed, valve 36 isopened to emit a plug of gas and product to the zone 40 between it andvalve 36 which is then closed. Valve 38 is then opened to deliver theproduct to an external recovery zone. Valve 38 is then closed to awaitthe next product recovery operation.

Finally, the fluidized bed reactor is equipped with an adequate ventingsystem to allow venting the bed during start up and shut down. Thereactor does not require the use of stirring means and/or wall scrapingmeans.

The highly active supported catalyst system of this invention appears toyield a fluid bed product having an average particle size between about0.005 to about 0.07 inches and preferably about 0.02 to about 0.04inches.

The feed stream of gaseous monomer, with or without inert gaseousdiluents, is fed into the reactor at a space time yield of about 2 to 10pounds/hour/cubic foot of bed volume.

The term virgin resin or polymer as used herein means polymer, ingranular form, as it is recovered from the polymerization reactor.

Certain of the catalysts of the present invention are capable ofproducing low density ethylene/hexene copolymers in a gas phase, fluidbed reactor, which copolymers are capable of being formed into filmshaving especially desirable properties. More particularly, thesecatalysts are prepared by heating silica at a temperature of at least600° C., e.g., from about 750° C. to about 850° C., for a period of timesufficient to remove physically and chemically bound water on the silicato the extent that from about 0.3 to about 0.7 mmoles of OH groups arepresent per gram of silica. This silica is then slurried in a liquidmedium and contacted with from about 1.1 to about 2.5 mmoles of aGrignard reagent in this liquid medium for a time and temperaturesufficient to permit dissolved organomagnesium to react with reactive OHgroups on the silica. The liquid is then evaporated, and the resultingdry, free-flowing powder is slurried in another liquid medium to becontacted with a tetravalent titanium compound, the number of moles ofthis tetravalent titanium compound being in excess of the number ofmoles of magnesium supported on the silica. For example, this molarratio of tetravalent titanium to supported magnesium may be from about 3to about 6.

Films having especially desirable properties may be formed with theabove-mentioned ethylene/hexene copolymers by a variety of techniques.For example, desirable blown films as well as slot cast films may beformed.

Blown films formed from ethylene/hexene copolymers having a density from0.920 to 0.927 g/cc may have especially desirable properties for bagstructures. For example, such blown films may be fabricated into trashbag structures which, when loaded to capacity, resist breaking whendropped from a height of, e.g., four feet. A particular example of ablown film formed from an ethylene/hexene copolymer having a density of0.927 and a melt index of 1 (ASTM D-1238, condition E), which is, inturn, formed in a gas phase, fluid bed reactor with a catalyst accordingto the present invention, is a blown film having a thickness of 1 mil, adart impact strength of at least 122 g, an MD Elmendorf tear strength ofat least 164 g/mil, a TD Elmendorf tear strength of at least 665 g/mil,a MD tensile strength of at least 6,400 lbs/in² and a TD tensilestrength of at least 5,400 lbs/in².

Slot cast films formed from low density ethylene/hexene copolymershaving a density of from about 0.916 to about 0.92 may have especiallydesirable properties as pallet stretch wrap. For example, such stretchwrap may hold loads together and onto pallets and resist breaking whensubjected to forces encountered in loading operations where loads aremoved about, dropped, etc. A particular example of a slot cast filmformed from an ethylene/hexene copolymer having a density of about 0.92and a melt index of 1.7 (ASTM D-1238, condition E), which is, in turn,formed in a gas phase, fluid bed reactor with a catalyst according tothe present invention, is a slot cast film having a thickness of 1 mil,an MD tensile strength of at least about 5,000 lbs/in², an ultimateelongation of at least 500 percent and a TD Elmendorf tear strength ofat least 600 g/mil.

The following Examples give examples of reactants and parameters whichmay be used in accordance with aspects of the present invention.

EXAMPLE 1

All procedures were carried out in glass or quartz equipment underpurified nitrogen using predried nitrogen purged solvents.

Davison silica gel, Grade 952, was dehydrated by fluidizing withnitrogen, heating at 200° C. for two hours and cooling to roomtemperature. This heated silica is believed to contain about 2 mmoles ofOH groups per gram of silica.

15 g of this product was slurried in 200 ml n-hexane. A 2.0 molarsolution of ethylmagnesium chloride in tetrahydrofuran (50 ml, 100mmoles) was added dropwise to the refluxing slurry over approximately 20minutes, after which time refluxing was continued for a further 30minutes. The solvents were distilled off, giving 29.5 g of dryfree-flowing powder.

15 g of this product (50.8 mmoles of Mg) was slurried in a 0.57 Molarsolution of TiCl₄ in heptane (150 ml, 85.5 mmoles) and refluxed for 45minutes, filtered, the solids washed with three 150 ml portions ofhexane and dried under vacuum. The titanium content of this solidcatalyst was 1.39 mmoles/g.

Slurry Polymerizations in n-Hexane 1. Ethylene, 1-ButeneCopolymerization

To 1.0 liter of pure dry n-hexane at 30° C. was added a 1.52M solutionof triethylaluminum (1.90 ml, 2.89 mmoles), 1-butene (50 g, 0.89 moles),hydrogen (0.06 moles) and the above catalyst (0.079 g, 0.11 mmoles Ti)giving an Al/Ti ratio of 26. Ethylene addition was begun andpolymerization conditions were adjusted to 80° C. and 120 psig totalpressure. After 30 minutes, under these conditions, ethylene additionwas stopped and the reactor cooled. Upon vacuum drying, a total of 195 gof polymer with a melt index (MI, I₂) of 53 and a density of 0.9166 g/ccwas obtained.

2. Ethylene, 1-Hexene Copolymerization

The copolymerization was carried out as in 1 using 2.4 ml (3.65 mmoles)of TEAL, 91 g 1-hexene (1.08 moles), hydrogen (0.033 moles) and 0.079 g(0.11 mmoles Ti), giving an Al/Ti ratio of 33. After drying, a total of150 g of polymer with a MI of 3.95 and a density of 0.9187 g/cc wasobtained.

COMPARATIVE EXAMPLE A

Several catalysts prepared substantially in accordance with theteachings of the Karol et al U.S. Pat. No. 4,302,566 were used incomparative testing as discussed in Examples given hereinafter. Thesecatalysts prepared substantially in accordance with this Karol et alpatent are referred to herein as "comparative A" catalysts or simply as"A" catalysts.

The comparative A catalysts are felt to be substantially equivalent tothe catalysts prepared according to the Examples of the Karol et alpatent. More particularly, these catalysts are felt to be substantiallyequivalent to those prepared by the following representative procedure.

In a 5 liter flask equipped with a mechanical stirrer, 16.0 g (0.168Mol) of anhydrous MgCl₂ is mixed with 850 ml of pure tetrahydrofuranunder nitrogen. The mixture is stirred at room temperature (˜25° C.)while 13.05 g (0.069 Mol) of TiCl₄ is added dropwise. After completeaddition, the contents of the flask are heated to reflux for aboutone-half to one hour to dissolve the solids. The system is cooled toroom temperature and 3 liters of pure n-hexane are slowly added over aperiod of one-half hour. A yellow solid precipitates. The supernatant isdecanted and the solids are washed with 3×one liter of n-hexane. Thesolids are filtered and dried in a rotating evaporating flask at 40°-60°C. to give 55 g of solid precursor composition.

The precursor composition may be analyzed at this point for Mg and Ticontent since some of the Mg and/or Ti compound may have been lostduring the isolation of the precursor composition. The empiricalformulas used herein in reporting these precursor compositions arederived by assuming that the Mg and the Ti still exist in the form ofthe compounds in which they are first added to the electron donorcompound and that all other residual weight in the precursor compositionis due to the electron donor compound.

Analysis of the solid would typically show the following percent byweight: Mg:6.1 percent, Ti:4.9 percent; which corresponds to TiMg₂.45Cl₈.9 (THF)₇.0. THF means tetrahydrofuran.

This precursor composition, which constitutes the catalytic portion ofthe comparative A catalyst, is supported on an inert silica carrier andactivated in accordance with the teachings of the Karol et al patent.

EXAMPLES 2-7

The catalysts of Examples 2-7 were prepared in two steps and the detailsare summarized in Table I, hereinbelow. The preparation of the catalystof Example 2 is felt to be representative of the preparation of thecatalysts of Examples 3-7 and is described below:

Step A

15 grams of Davison silica gel (dried at 200° C. for 4 hours) wereplaced into a 500 ml 4-neck reaction flask fitted with a droppingfunnel, water condensor, dry nitrogen line, and overhead stirrer. Undera slow nitrogen purge, 200 ml of dry hexane was added to the silicawhile stirring. The silica/hexane slurry was brought to refluxtemperature and 50 ml of 2.0M EtMgCL/THF solution was added dropwise(about 15 minutes) and the reflux was continued for an additional 30minutes. After this time, the solvents were removed by distillation andthe silica dried at ˜80° C. under a nitrogen purge. Total yield, 29grams; Mg (Theory) 3.45 mmols/gm.

Step B

15 grams of Step A reaction product (51.7 mmols of Mg) were placed intoa 500 ml reaction flask (apparatus as described above). 200 ml ofn-heptane containing 10.0 ml (91 mmols) of TiCl₄ was added to the flaskwhile stirring. The slurry was refluxed for 45 minutes. After this time,the slurry was cooled to room temperature, transferred to a filter flask(under nitrogen), filtered, washed with four 100 ml portions of hexaneand dried under nitrogen purge; Mg (found) 1.65 mmols/gm, Mg (Theory)1.67; Ti (found) 1.24 mmols/gm.

In addition, for comparison reasons, Example 5 was repeated with themolar ratio of TiCl₄ added in Step B to the magnesium present on thesilica being less than 1. The resultant catalyst and the processingdetails are indicated in Table I as Example 5 (Comparative).

                                      TABLE I                                     __________________________________________________________________________    CONDITIONS USED TO PREPARE CATALYSTS                                          __________________________________________________________________________                STEP A                                                                 Dehydration                                                                              (a)                Mg                                         Example                                                                            Temperature                                                                          GMS mmols                                                                             mmols                                                                              Mg  Product                                                                             mmols/gm                                   Number                                                                             °C.                                                                           Silica                                                                            SiOH                                                                              RMg ×                                                                        SiOH                                                                              Wt. (gms)                                                                           (Theory)                                   __________________________________________________________________________    2    200    15.0                                                                              45  100  2.2 29.0  3.45                                       3    200    15.0                                                                              45  40   0.9 19.5  2.05                                       4    200    15.0                                                                              45  20   0.4 16.7  1.20                                       5    600    15.0                                                                              22  20   0.9 17.4  1.15                                       6    800    25.0                                                                              12  10   0.8 26.5  0.38                                       7    800    15.0                                                                              15  100  6.7 32.7  3.06                                       __________________________________________________________________________    STEP B                                                                        GMS                     mmols/GM                                              Example                                                                             Step (A)                                                                           mmols                                                                             mmols                                                                             Product                                                                            Mg  Mg   Ti                                           Number                                                                              Product                                                                            Mg  Ti  Wt.  (found)                                                                           (theory)                                                                           (found)                                                                           Mg/Ti                                    __________________________________________________________________________    2     15.0 51.7                                                                              91.1                                                                              18.0 2.93                                                                              2.87 1.51                                                                              1.9                                      3     15.0 30.7                                                                              91.1                                                                              18.4 1.65                                                                              1.67 1.24                                                                              1.3                                      4     15.0 17.9                                                                              91.1                                                                              18.2 0.81                                                                              0.99 1.19                                                                               0.69                                    5     15.0 17.2                                                                              91.1                                                                              17.9 0.96                                                                              0.96 0.72                                                                              1.3                                      6     15.0  5.7                                                                              45.6                                                                              16.2 0.37                                                                              0.35 0.39                                                                               0.95                                    7     15.0 45.9                                                                              91.1                                                                              20.3 1.98                                                                              2.26 1.59                                                                              1.2                                      __________________________________________________________________________     (a)Surface hydroxyl concentration of silica dried at various temperatures     were taken from: J. B. Peri and A. L. Hensley, Jr., J. Physical Chem., 72     (8), 2926 (1968)                                                         

Catalysts were initially tested in a 1.6 liter slurry reactor and in arepresentative experiment, 1.0 liter of hexane and about 100 ml of1-hexane (62.5 gms) were added to the autoclave while at ambienttemperature. 0.047 gms of catalyst (0.06 mmols of Ti) was slurried intoabout 50 ml of hexane to which was added sufficient triethyl aluminum togive an Al/Ti ratio of 40. This catalyst slurry was transferred to thereactor using slight nitrogen pressure and 0.03 moles of hydrogen wereadded by measuring through a calibrated Hoke bomb.

The stirring rate was adjusted to 1000 rpm and the temperature controlunit set to 80° C. Ethylene pressure was introduced when the autoclavereached 40° C., and the total reactor pressure was adjusted to 115 psi.

Polymerizations were continued for 25-35 minutes in order to produce130-150 grams of polymer.

About 400 ppm of Irganox 1076 was added to the polymer/hexane slurry andthe hexane was allowed to evaporate under a hood. The products wereplaced into a vacuum oven overnight at approximately 60° C. to removeresidual hexane and monomer.

FIG. 2 shows the change in the copolymerization properties of thecatalysts of Examples 2-4, as well as comparative A, as measured byresin density at the 1-3 I₂ melt index level over a range of magnesiumloadings into Davison 952 silica dried at 200° C.

If silica dried at 800° C. is used in place of silica dried at 200° C.,the copolymerization properties of the catalysts may vary. It is notedthat silica dried at 200° C. contains about 6 SiOH Groups/100 Angstrom²while silica dried at 800° C. contains only about 1 SiOH group/100Angstrom².

Ethylene/1-butene copolymers were prepared under similar conditions withboth comparative A catalyst and the Example 2 catalyst. Table IIsummarizes the polymerization conditions and product properties of C₂/C₄ copolymers prepared with A and Example 2 catalysts. Examination ofthe data in Table II indicates that under similar polymerizationconditions the Example 2 catalyst produced a lower density product thanthe A catalyst.

                  TABLE II*                                                       ______________________________________                                        POLYMERIZATION CONDITIONS AND PRODUCT                                         DATA FOR C.sub.2 /C.sub.4 COPOLYMERS PREPARED                                 WITH A AND EXAMPLE 2 CATALYSTS                                                Experi-                                                                             Conditions**         Product                                            ment  Catalyst               Gms   I.sub.2 gms/                                                                         Density                             No.   Type     H.sub.2 /C.sub.4                                                                      C.sub.4 /C.sub.2                                                                    Butene                                                                              10 min.                                                                              gms/cc                              ______________________________________                                        1     A        0.13    2.1   50    23     0.932                               2     A        0.13    2.0   48    9.0    0.933                               3     A        0.13    1.9   50    10     0.929                               4     Ex. 2    0.13    2.1   50    61     0.917                               5     Ex. 2    0.13    2.1   50    53     0.917                               6     Ex. 2    0.06    1.1   30    1.7    0.925                               7     A        0.06    0.9   30    2.1    0.934                               8     A        0.06    0.9   30    1.5    0.931                               9     Ex. 2    0.06    0.9   30    1.1    0.929                               10    A        0.05    1.5   48    2.3    0.929                               11    Ex. 2    0.05    1.5   48    1.1    0.925                               12    A        0.10    1.9   47    2.4    0.926                               13    Ex. 2    0.06    1.6   49    1.8    0.920                               14    A        0.05    2.1   64    1.0    0.919                               15    A        0.08    2.2   64    2.3    0.921                               16    Ex. 2    0.07    2.2   66    1.3    0.908                               17    Ex. 2    0.05    1.8   53    3.6    0.912                               18    Ex. 2    0.06    1.9   53    4.7    0.913                               19    Ex. 2    0.05    1.7   55    2.9    0.917                               20    Ex. 2    0.05    1.6   50    2.6    0.920                               ______________________________________                                         *Data illustrated in FIG. 2.                                                  **Other conditions: 80° C., 1.01 Hexane, 1000 rpm, ˜0.08         moles of titanium in 1.6 liter reactor.                                  

For example, comparison of experiments 1 and 5 in Table II shows thatthe A catalyst produced a product with a density of 0.932 gms/cc whilethe Example 2 catalyst product exhibited a density of 0.917 gms/cc. Boththe A and Example 2 catalysts require comparable amounts of hydrogen toproduce a product with a melt index of about 1-2 (compare experiments 8and 9). However, at higher hydrogen levels, the Example 2 catalystproducts produces a much higher melt index product than A (compareexperiments 4 and 3 in Table II).

FIG. 3 illustrates the copolymerization differences between the A andExample 2 catalysts. FIG. 3 shows the density versus the butene/ethyleneratio for each of these catalysts.

Examination of FIG. 3 suggests that a 0.918 gm/cc LLDPE product requiresa C₄ /C₂ ratio of about 2.7 for A catalyst while the Example 2 catalystrequires only a ratio of 1.7. This corresponds to 35 percent less butenein the reactor for the Example 2 catalyst.

Table III and FIG. 4 summarize the polymerization conditions and productproperties of the ethylene/1-hexane copolymers prepared with A, Example2 and 3 catalysts in a 1.6 liter slurry reactor. The Example 3 catalystcontains less magnesium and exhibits better copolymerization propertiesthan the Example 2 catalyst.

                  TABLE III*                                                      ______________________________________                                        POLYMERIZATION CONDITIONS AND PRODUCT                                         DATA FOR C.sub.2 /C.sub.6 COPOLYMERS PREPARED                                 WITH Ex. 3, Ex. 2 and A CATALYSTS                                             Exper-                                                                              Conditions**         Product                                            iment Catalyst               Gms   I.sub.2 gms/                                                                         Density                             No.   Example  H.sub.2 /C.sub.6                                                                      C.sub.6 /C.sub.2                                                                    Hexene                                                                              10 min.                                                                              gms/cc                              ______________________________________                                        21    A        0.05    1.0   49    1.2    0.937                               22    2        0.05    1.0   49    2.9    0.932                               23    3        0.05    1.2   60    1.9    0.920                               24    3        0.05    1.2   57    2.4    0.924                               25    3        0.05    1.3   64    2.1    0.918                               26    A        0.05    1.6   75    1.2    0.935                               27    A        0.06    1.7   87    1.6    0.933                               28    2        0.05    1.5   72    2.2    0.924                               29    3        0.05    1.7   86    3.6    <0.905                              30    2        0.05    2.1   92    1.2    0.918                               31    A        0.05    2.5   120   1.9    0.929                               32    3        0.06    1.8   91    3.9    0.919                               ______________________________________                                         *Data illustrated in FIG. 4.                                                  **Other conditions: 80° C., 1.01 Hexane, 1000 rpm, ˜0.08         mmols of titanium in 1.6 liter reactor total pressure 120 psi.           

Examination of FIG. 4 clearly shows that the copolymerization propertiesof these three catalysts are Example 3>Example 2>A. At a 1-hexane toethylene ratio of about 1.3, the Example 2, Example 3 and A catalystsproduced resins with densities of about 0.918 gm/cc, 0.927 gms/cc and0.935 gms/cc, respectively.

The Example 3 catalyst requires about 50 percent (±10 percent) less1-hexene in the reactor than A catalyst to produce a LLDPE material witha density of about 0.920 gm/cc.

Catalysts were utilized in a two gallon slurry laboratory reactor sothat sufficient quantities of polymer (500-800 gms) could be preparedfor evaluation. Table IV and FIG. 5 summarize the polymerizationconditions and product properties of ethylene/1-hexene copolymersprepared with catalysts of Examples 3, 5, 6, 7 and A. Examination ofFIG. 5 suggests that the relative copolymerization properties of thesecatalysts are (Example 3, Example 5)>Example 6>Example 7>A. However, thedifferences between Example 3, Example 5 and Example 6 are relativelysmall (±10 percent) and may not be statistically significant.

                  TABLE IV                                                        ______________________________________                                        POLYMERIZATION CONDITIONS AND PRODUCT                                         DATA FOR C.sub.2 /C.sub.6 COPOLYMERS PREPARED                                 IN THE TWO GALLON REACTOR                                                     Exper-                                                                              Conditions       Product                                                iment Catalyst gms           I.sub.2 gms/                                                                         Density                                                                              Yield                              No.   Example  Hexene  C.sub.6 /C.sub.2                                                                    10 min.                                                                              gms/cc gms                                ______________________________________                                        33    3        270     1.05  0.9    0.928  604                                34    3        310     1.25  1.0    0.925  435                                35    3        440     1.84  1.2    0.918  575                                36    5        316     1.34  --     0.923  485                                37    5        382     1.66  2.0    0.920  444                                38    5        380     1.56  --     0.919  460                                39    7        671     28.5  1.7    0.924  668                                40    6        391     1.58  0.4    0.928  330                                41    6        412     1.66  0.2    0.925  500                                42    6        405     1.72  0.4    0.927  409                                43    6        438     1.86  0.6    0.926  460                                44    A        410     1.68  0.6    0.935  506                                45    A        441     1.87  1.0    0.933  540                                46    A        644     2.74  0.9    0.929  655                                47    A        1006    4.5   3.2    0.919  715                                ______________________________________                                    

The catalyst of Example 2 may generate about four times as much heat(per area of catalyst particle) as the Example 6 catalyst. This extraheat could result in severe temperature gradients within certain fluidbed reactors and poor operability and/or bulk density. Therefore, evenin gas phase, fluidized bed arrangements which cannot optimallyaccommodate relatively high heat generating catalysts, such as theExample 2 catalyst, such fluidizing bed arrangements may readilyaccommodate relatively low heat generating catalysts, such as theExample 6 catalyst, without encountering problems of severe temperaturegradients, poor operability and/or poor bulk density.

The data used for FIG. 2 is summarized in Table V as follows.

                  TABLE V                                                         ______________________________________                                        DATA USED FOR FIG. 2                                                          Experiment                                                                            Catalyst  Gms                                                         No.     Example   Hexene-  C.sub.6 /C.sub.2                                                                     Density I.sub.2                             ______________________________________                                        48      A         87       1.73   .9328   1.65                                49      A         76       1.60   .9351   1.21                                50      2         91       1.84   .9187   3.95                                51      2         72       1.53   .9241   2.22                                52      2         87.5     1.86   .9194   1.50                                53      2         84.5     1.78   .9178   4.86                                54      3         86       1.68   <.905   3.59                                55      3         90.5     1.92   <.905   7.31                                56      4         88       1.86   .9247   1.04                                57      4         91       1.93   .9253   2.86                                ______________________________________                                    

The performance of scaled up version of the catalyst of Example 6(essentially the same as the aforementioned version except that the Mgloading in step A is 0.53 mmoles of mg instead of 0.38 mmoles/g) and Acatalysts were compared under nearly identical operating conditions in afluidized-bed, pilot reactor. This comparison was accomplished keepingtwo important operating variables constant, namely temperature, and themolar ratio of hexene to ethylene in the gas phase, and then observingthe physical properties of the resin product under these comparableconditions.

The experiments were done in a pilot-scale fluidized-bed reactor whichis 18 inches in diameter and capable of producing up to 50 lb/hr ofresin. The catalysts used for the comparison were A and the catalyst ofExample 6 which was prepared at a pilot plant. The only differencebetween the pilot plant preparation of the catalyst of Example 6 and thelaboratory procedure (described earlier) was that a solvent decantationfollowed by several solvent washes was substituted for the filtration inStep B. Details of the comparison are found in Table VI, and support theslurry reactor findings that the catalyst of Example 6 has significantlyimproved copolymerization properties compared to A when run undersimilar reactor conditions.

                  TABLE VI                                                        ______________________________________                                        COMPARISON OF EX. 6 AND A IN                                                  A GAS PHASE REACTOR                                                                          Ex. 6*      A                                                                 Exper-  Exper-  Exper-                                                        iment 1 iment 2 iment 1                                        ______________________________________                                        Reaction temperature                                                                           85° C.                                                                           85° C.                                                                         85° C.                              Hexene/ethylene molar                                                                          .123      .107    .11-.12                                    ratio in gas phase                                                            Hydrogen/ethylene molar                                                                        .207      .209    .21-.22                                    ratio in gas phase                                                            Physical Properties                                                           Melt Index       1.69      1.28    1.6                                        Density          .9201     .9247   0.934                                      ______________________________________                                         *[Mg] = 0.53 mmols/g;                                                         [Ti] = 0.50 mmols/g.                                                     

The hexene copolymer samples were extruded into film at standardconditions on a Brabender blown film line. The system comprises a 3/4inch extruder feeding a one inch diameter blown film die. The die gapwas 0.39 inches. Extrusion rate for all samples was 2.4 lb/hr, at a melttemperature of 185° to 195° C. The film was extruded at a thickness of1.5 mils, with a 2:1 blowup ratio and a 21/4 inch frost line height. Allresin samples were stabilized with the same formulation; 700 ppmKemamine AS 990 to neutralize catalyst residues, 200 ppm Irganox 1010hindered phenolic antioxidant, and 200 ppm Weston 399 phosphite typeperoxide decomposer.

Physical properties were then run on the film in the product developmentlaboratory. The values obtained in the laboratory are not in strictaccordance with ASTM testing procedures, since the laboratorytemperature and relative humidity are not controlled. The valuesreported are of merit in an approximate relative sense. Table VII liststhe film properties measured on the A and Example 6 catalyzed samplesprepared in the fluid bed pilot plant. MD tear strength is a measure ofthe resistance of the film to the propagation of a tear initiated in themachine direction of the film. TD tear measures the resistance of thefilm to the propagation of a tear initiated in the transverse directionof the film. Impact strength measures the amount of energy absorbedduring a high speed puncture of the film. These tests are felt to be ofsignificant value in the ranking of relative toughness.

                  TABLE VII                                                       ______________________________________                                        FILM PROPERTIES                                                                                    Tear Strength  Impact                                    Catalyst Head        (gm/mil)       Strength                                  Type Used                                                                              Pressure (psig)                                                                           MD      TD       (gm/mil)                                ______________________________________                                        A        2700         60     230      279                                     A        2600         71     222      292                                     Ex. 6    2500        234     586      557                                     Ex. 6    2800        167     564      562                                     ______________________________________                                    

The improvement in properties of the Example 6 catalyzed hexenecopolymers is due essentially to the improved comonomer incorporation,which results in a significantly lower density at the same reactorconditions.

It can easily be seen from the data in Table VII that the Example 6catalyzed samples (produced at reactor conditions which bracket those ofthe A catalyzed samples) are much tougher in these tests than the Acatalyzed samples. Impact strength of the Example 6 catalyzed samples isnearly double that of the A catalyzed samples. TD tear strength is morethan 2.5 times that of the A samples, and MD tear strength averages morethan 3 times that of the A samples. The melt indices of these sampleswere all similar, between 1.3 and 1.7. Head pressure readings indicatethat the processability of the A and Example 6 resins are essentiallythe same.

COMPARATIVE EXAMPLE B

The catalyst of this Comparative Example was prepared in accordance withExample 7 of the Yamaguchi et al U.S. Pat. No. 3,989,881. One willreadily note the similarities between this comparative Example Bcatalyst composition and the catalytically active precursor compositiondescribed in the Karol et al U.S. Pat. No. 4,302,566, e.g., exemplifiedin the passage extending from line 65 of column 14 to line 26 of column15.

The particular procedure used to prepare the catalyst of comparativeExample B is as follows.

15 g (158 mmol) of anhydrous magnesium chloride, MgCl₂, was slurried in530 ml dry tetrahydrofuran (THF) in a one liter 3-necked round-bottomedflask fitted with a magnetic stirrer.

10 g (52.7 mmol) of TiCl₄ were added dropwise while heating. The mixturewas refluxed for approximately one hour, by which time all solids haddissolved. After cooling, 275 ml hexane were added dropwise at 5ml/minute to precipitate the solids. The mother-liquors were decantedand the solid washed with two 200 ml portions of hexane by decantation,and dried. The yellow solid contained 3.08 mmol Mg and 0.95 mmol Ti/gcatalyst.

EXAMPLES 8-9

All procedures were carried out in glass or quartz equipment underpurified nitrogen using predried nitrogen purged solvents.

Davison silica gel, Grade 952, was dehydrated by fluidizing withnitrogen, heating at 800° C. for 16 hours and cooled to room temperatureunder nitrogen.

A portion of the activated silica, as given in Table VIII, wasintroduced into a 500 ml 4-necked round-bottomed flask fitted with astirrer, thermometer, addition funnel, dry nitrogen line and adistillation head to remove solvent. The flask was placed in an oil bathmaintained at a controlled temperature.

250 ml hexane was added to the silica while stirring under a slownitrogen purge. The silica/hexane slurry was brought to refluxtemperature and a 2.0M solution of ethylmagnesium chloride in THF addeddropwise over 5-15 minutes. The reflux was continued for an additional30-40 minutes. After a total of 45 minutes the solvents were removed bydistillation and the silica dried at approximately 80° C. under anitrogen purge. 15 g of this product was slurried in 45.5 mmols of TiCl₄dissolved in 200 ml n-heptane, and the slurry refluxed for 45 minutes,using the same apparatus as described above. The mixture was allowed tocool to room temperature, transferred to a filter flask under N₂ andfiltered. The solids were washed with three to four 100-150 ml portionsof hexane and dried under a nitrogen purge. A free flowing yellow powderwas obtained. Analyses for Ti and Mg are given in Table VIII.

COMPARATIVE EXAMPLE C

A catalyst was prepared in substantially the same manner as describedfor Examples 8 and 9 except that the silica support was omitted. Furtherdetails are given in Table VIII. It is noted that the formation of asmall amount of precipitate as evidenced by cloudiness was noticed asGrignard was added to hexane. This observation would have been masked ifsilica were present as a hexane slurry.

EXAMPLES 10-11

Catalysts prepared in the pilot plant were scaled up directly fromlaboratory preparations, except that decantation had to be used to washthe final catalyst rather than filtration, as described above.

Further preparation details are given in Table VIII.

                                      TABLE VIII                                  __________________________________________________________________________    DETAILS OF CATALYST PREPARATION                                               Example                                                                            SiO.sub.2 *                                                                       MgCl.sub.2                                                                         EtMgCl/THF                                                                            TiCl.sub.4                                                                         Analysis (mmols/g final Cat.)                      Number                                                                             (g) (mmols)                                                                            (mmols) (mmols)                                                                            Mg   Ti Mg/Si--OH***                               __________________________________________________________________________     8    25 --   10.0     45.5**                                                                            0.37 0.39                                                                             0.77                                        9    17 --   20.0     45.5**                                                                            0.92 0.81                                                                             2.26                                       10   602 --   400     1821 0.53 0.50                                                                             1.28                                       11   500 --   400     1593 0.75 0.54                                                                             1.54                                       B    --  157.4                                                                              --      52.8 3.66 0.95                                                                             --                                         C    --  --   20.0    45.5 --   1.42                                                                             --                                         __________________________________________________________________________     *SiO.sub.2 dried at 800° C. for 16 hours.                              **The given amount of TiCl.sub.4 was reacted with 15 g of the SiO.sub.2       /EtMgCl reaction product.                                                     ***[Si--OH] of SiO.sub.2 = 0.52 mmols/g.                                 

A two gallon autoclave was heated under a pure nitrogen purge to about90° C. for 0.5 hour to clean out remaining moisture, and then cooled toambient temperature.

Five liters of prepurified hexane and the desired amount of 1-hexanewere added to the reactor and the mixture stirred at approximately 900rpm. The catalyst was activated in a catalyst addition flask by addingan amount of 25 weight percent triethylaluminum in hexane to a givenweight of catalyst suspended in 50 ml of dry hexane. Amounts used aregiven in Tables IX and X. The mixture was pressured into the reactorusing nitrogen and the total reactor pressure adjusted to 20 psig withhydrogen. The reactor was heated at 3° C./minute with a set-point at 80°C. Ethylene was introduced at 60° C. so as to maintain total operatingpressure at 120 psig. Polymerizations were carried out for approximatelyone hour, giving 450-950 g of polymer.

                                      TABLE IX                                    __________________________________________________________________________    COMPARISON OF EX. 8 CATALYST WITH B AND C                                     Run Identification                                                                      Polymerization Conditions**                                                                            Product Obtained                           Catalyst  Cat. Wt. H.sub.2                                                                     Total P                                                                            TEAL*                                                                              Al/Ti                                                                             Hexene                                                                            Density                                                                            I.sub.2                                                                             Yield (g)                       Ex. No.                                                                            Run No.                                                                            (g) (psi)                                                                            (psig)                                                                             (mmol)                                                                             ratio                                                                             (g) (g/cc)                                                                             (g/10 min)                                                                          Run Time (hrs)                  __________________________________________________________________________    8    1    0.50                                                                              15 120  7.6  39  412 0.9250                                                                             0.2   500 (1.0)                            2    0.70                                                                              25 120  10.8 40  550 0.9237                                                                             1.1   560 (0.8)                            3    0.73                                                                              25 122  11.4 40  622 0.9216                                                                             1.0   537 (0.5)                       B    4    0.197                                                                             15 105  7.1  38  417 0.9322                                                                              0.12 450 (2.0)                            5    0.151                                                                             20 110  6.0  42  644 0.9292                                                                              0.90 655 (1.0)                            6    0.168                                                                             20 110  6.8  42  1006                                                                              0.9188                                                                             3.2   715 (1.0)                       C    7    0.160                                                                             25 120  9.1  41  449 0.9379                                                                              0.86 525 (2.0)                       __________________________________________________________________________     *25 weight percent triethylaluminum in hexane = 1.54 M.                       **Polymerization Temperature: 80° C.                              

                                      TABLE X                                     __________________________________________________________________________    EFFECT OF Mg LOADING ON COPOLYMERIZATION                                                   Ratio of                                                         Example                                                                             Mg     Mg to                                                                              Cat. Wt.                                                                           H.sub.2                                                                           Total P                                                                            TEAL.sup.(b)                                                                       Al/Ti                                                                              Hexene                                                                            Density                                                                            I.sub.2                                                                             Yield (g)            No.   (mmol/g)                                                                             SiOH.sup.(d)                                                                       (g)  (psi)                                                                             (psig)                                                                             (mmol)                                                                             ratio                                                                              (g) (g/cc)                                                                             (g/10                                                                               Run                  __________________________________________________________________________                                                             (hrs)                 8    0.37   0.77 0.51 15  120   8.0 40   438 0.9274                                                                             0.40  460 (0.9)             9    0.92   2.26 0.81 15  120  12.3 19   446 0.9162                                                                             1.73  950 (0.6)            10    0.53   1.28 0.80 15  120  12.3 31   451 0.9252                                                                             0.34  821 (1.0)            11    0.75   1.54 0.80 15  120  12.3 28   451 0.9239                                                                             0.76  883 (0.6)            B     3.08.sup.(c)                                                                         --    0.197                                                                             15  105   7.1 38   4.17                                                                              0.9322                                                                             0.12  450                  __________________________________________________________________________                                                             (2.0)                 .sup.(a) 80° C.; 5.0 liters hexane.                                    .sup.(b) 25 wt. percent triethylaluminum in hexane = 1.54 M.                  .sup.(c) Unsupported.                                                         .sup.(d) Surface hydroxyl concentration of silica dried at 800° C.     taken as 0.52 mmols/g. See J. B. Peri and A. L. Hensley, Jr., J. Phys.        Chem., 72 (8), 2926 (1968)                                               

The catalyst of Example 10 was used in a pilot plant, gas phase, fluidbed reactor operating at 85° C. to copolymerize hexene/ethylene at a H₂/C₂ mole ratio of 0.212 and c₆ /C₂ mole ratio of 0.126.

Activation of the catalyst was carried out in the fluid bed reactorusing a 5 weight percent solution of triethylaluminum in isopentanesufficient to give and Al/Ti molar ratio in the reactor of 20-50 and thepolymerization was allowed to reach equilibrium under continuousoperation. The product obtained had a density of 0.920 g/cc and a meltindex I₂ =1.69 g/10 mins.

As used herein, the term "magnesium" will be understood to connote,especially, chemically combined forms of magnesium as opposed to merelyuncombined, elemental forms thereof.

The disclosures of each of the referenced publications, including U.S.Patents, identified hereinabove, are incorporated into thisspecification by reference.

The present invention may comprise, consist essentially of or consist ofthe elements or method steps referred to herein.

What is claimed is:
 1. A process for preparing a supported catalystcomposition for use in alpha-olefin polymerization reactions, saidprocess consisting essentially of the steps of:(i) contacting a solid,porous carrier having reactive OH groups with a liquid, said liquidcontaining at least one organomagnesium composition having the empiricalformula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R is a C₁ -C₁₂ hydrocarbyl group, R' is a halogen, and n is arational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to obtain a carrier, containing magnesium, in theform of a dry, free-flowing powder; and (iii) reacting said powder ofstep (ii) with at least one transition metal compound in a liquidmedium, the number of moles of said transition metal compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said transition metal compound being soluble in said liquid medium,and the magnesium being substantially insoluble in said liquid medium,whereby a reacted form of transition metal which is insoluble in saidliquid medium becomes supported on said carrier.
 2. A process accordingto claim 1, wherein said solid, porous carrier is contacted with saidliquid step (i) in the absence of ball milling.
 3. A process accordingto claim 2, wherein R is unsubstituted C₁ -C₁₂ alkyl, R' is Cl, Br or Iand n is
 1. 4. A process according to claim 3, wherein said contactingstep (i) comprises:(a) slurrying said carrier in a non-Lewis baseliquid; and (b) adding said organomagnesium composition to said slurryof step (a) in the form of an ether solution of said organomagnesiumcomposition.
 5. A process according to claim 4, wherein said solid,porous carrier is substantially composed of silica, alumina orcombinations thereof.
 6. A process according to claim 5, wherein saidsolid porous carrier is silica having from about 0.3 to about 0.7mmoles/gram of said OH groups.
 7. A process according to claim 6wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 1.1 to about 2.5.
 8. A process according toclaim 7 wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 1.5 to about 2.5.
 9. A process according toclaim 8, wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 2.0 to about 2.5.
 10. A catalyst compositionfor use in alpha-olefin polymerization reactions prepared by a processconsisting essentially of the steps of:(i) contacting a solid, porouscarrier having reactive OH groups with a liquid, said liquid containingat least one organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R is a C₁ -C₁₂ hydrocarbyl group, R' is a halogen, and n is arational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to obtain a carrier, containing magnesium, in theform of a dry, free-flowing powder; and (iii) reacting said powder ofstep (ii) with at least one transition metal compound in a liquidmedium, the number of moles of said transition metal compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said transition metal compound being soluble in said liquid medium,and said magnesium of said carrier being substantially insoluble in saidliquid medium, whereby a reacted form of transition metal which isinsoluble in said liquid medium becomes supported on said carrier.
 11. Acatalyst composition of claim 10 wherein said solid, porous carrier iscontacted with said liquid in step (i) in the absence of ball milling.12. A catalyst composition of claim 11 wherein R is unsubstituted C₁-C₁₂ alkyl, R' is Cl, Br or I and n is
 1. 13. A catalyst composition ofclaim 12, wherein said contacting step (i) comprises:(a) slurrying saidcarrier in a non-Lewis base liquid; and (b) adding said organomagnesiumcomposition to said slurry of step (a) in the form of an ether solutionof said organomagnesium composition.
 14. A catalyst composition of claim13, wherein said solid, porous carrier is substantially composed ofsilica, alumina or combinations thereof.
 15. A catalyst composition ofclaim 14 wherein said solid porous carrier is silica having from about0.3 to about 0.7 mmoles/gram of said OH groups.
 16. A catalystcomposition of claim 15 wherein, in step (i), the ratio of the number ofmoles of said organomagnesium composition to the number of moles of saidOH groups on said silica is from about 1.1 to about 2.5.
 17. A catalystcomposition of claim 16 wherein, in step (i), the ratio of the number ofmoles of said organomagnesium composition to the number of moles of saidOH groups on said silica is from about 1.5 to about 2.5.
 18. A catalystcomposition of claim 17, wherein, in step (i), the ratio of the numberof moles of said organomagnesium composition to the number of moles ofsaid OH groups on said silica is from about 2.0 to about 2.5.
 19. Acomposition of matter prepared by a process consisting essentially ofthe steps of:(i) contacting a solid, porous carrier having reactive OHgroups with a liquid, said liquid containing at least oneorganomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

wherein R is a C₁ -C₁₂ hydrocarbyl group, R' is a halogen, and n is arational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; and (ii) evaporatingsaid liquid from step (i) to obtain a carrier, containing magnesium, inthe form of a dry, free-flowing powder.
 20. A composition of claim 19,wherein said solid, porous carrier is contacted with said liquid in step(i) in the absence of ball milling.
 21. A composition of claim 20,wherein R is unsubstituted C₁ -C₁₂ alkyl, R' is Cl, Br or I and n is 1.22. A composition of claim 21, wherein said contacting step (i)comprises:(a) slurrying said carrier in a non-Lewis base liquid; and (b)adding said organomagnesium composition to said slurry of step (a) inthe form of an ether solution of said organomagnesium composition.
 23. Acomposition of claim 22, wherein said solid, porous carrier is silica,alumina or combinations thereof.
 24. A composition of claim 23, whereinsaid solid porous carrier is silica having from about 0.3 to about 0.7mmoles/gram of said OH groups.
 25. A composition of claim 24, wherein,in step (i), the ratio of the number of moles of said organomagnesiumcomposition to the number of moles of said OH groups on said silica isfrom about 1.1 to about 2.5.
 26. A composition of claim 25, wherein, instep (i), the ratio of the number of moles of said organomagnesiumcomposition to the number of moles of said OH groups on said silica isfrom about 1.5 to about 2.5.
 27. A composition of claim 26, wherein, instep (i), the ratio of the number of moles of said organomagnesiumcomposition to the number of moles of said OH groups on said silica isfrom about 2.0 to about 2.5.
 28. A composition of claim 27, whereinchemically and physically bound water has been removed from said silicain step (i) by heating at a temperature from about 750° C. to about 850°C. for at least four hours, and the organomagnesium composition offormula (I) is C₂ H₅ MgCl.
 29. A process for preparing a supportedcatalyst composition for use in alpha-olefin polymerization reactions,said process consisting essentially of the steps of:(i) contacting asolid, porous carrier having reactive OH groups with a liquid in theabsence of ball milling, said liquid containing at least oneorganomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R is a C₁ -C₁₂ hydrocarbyl group, R' is a halogen, and n is arational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to precipitate magnesium onto said carrier, saidprecipitated magnesium being selected from the group consisting ofmagnesium dihalide, unreacted organomagnesium and mixtures thereof,whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and (iii) reacting said powder of step(ii) with at least one tetravalent titanium compound in a liquid medium,the number of moles of said tetravalent titanium compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said tetravalent titanium compound being soluble in said liquidmedium, and said supported magnesium composition being substantiallyinsoluble in said liquid medium, whereby a reacted form of titaniumwhich is insoluble in said liquid medium becomes supported on saidcarrier.
 30. A process according to claim 29, wherein R is unsubstitutedC₁ -C₁₂ alkyl, R' is Cl, Br or I and n is
 1. 31. A process according toclaim 30, wherein said contacting step (i) comprises:(a) slurrying saidcarrier in a non-Lewis base liquid; and (b) adding said organomagnesiumcomposition to said slurry of step (a) in the form of an ether solutionof said organomagnesium composition.
 32. A process according to claim31, wherein said solid, porous carrier is substantially composed ofsilica, alumina or combinations thereof.
 33. A process according toclaim 32, wherein said tetravelent titanium compound is TiCl₄.
 34. Asupported catalyst composition for use in alpha-olefin polymerizationreactions, prepared by a process consisting essentially of the stepsof:(i) contacting a solid, porous carrier having reactive OH groups witha liquid in the absence of ball milling, said liquid containing at leastone organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R is a C₁ -C₁₂ hydrocarbyl group, R' is a halogen, and n is arational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to precipitate magnesium onto said carrier, saidprecipitated magnesium being selected from the group consisting ofmagnesium dihalide, unreacted organomagnesium and mixtures thereof,whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and (iii) reacting said powder of step(ii) with at least one tetravalent titanium compound in a liquid medium,the number of moles of said tetravalent titanium compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said tetravalent titanium compound being soluble in said liquidmedium, and said supported magnesium composition being substantiallyinsoluble in said liquid medium, whereby a reacted form of titaniumwhich is insoluble in said liquid medium becomes supported on saidcarrier.
 35. A supported catalyst composition of claim 34 wherein R isunsubstituted C₁ -C₁₂ alkyl, R' is Cl, Br or I and n is
 1. 36. Asupported catalyst composition of claim 35, wherein, in step (i), theratio of the number of moles of said organomagnesium composition to thenumber of moles of said OH groups on said silica is from about 1.1 toabout 2.5.
 37. A supported catalyst composition of claim 36 wherein, instep (i), the ratio of the number of moles of said organomagnesiumcomposition to the number of moles of said OH groups on said silica isfrom about 1.5 to about 2.5.
 38. A supported catalyst composition ofclaim 37 wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 2.0 to about 2.5.
 39. A process for preparinga supported catalyst composition for use in alpha-olefin polymerizationreactions, said process consisting essentially of the steps of:(i)contacting, in the absence of an organoaluminum or aluminum halidecompound, a solid, porous carrier having reactive OH groups with aliquid, said liquid containing at least one organomagnesium compositionhaving the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different C₁ -C₁₂ hydrocarbyl groups, andn is a rational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to obtain a carrier, containing magnesium, in theform of a dry, free-flowing powder; and (iii) reacting said powder ofstep (ii) with at least one transition metal compound in a liquidmedium, the number of moles of said transition metal compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said transition metal compound being soluble in said liquid medium,and the magnesium being substantially insoluble in said liquid medium,whereby a reacted form of transition metal which is insoluble in saidliquid medium becomes supported on said carrier.
 40. A process accordingto claim 39, wherein said solid, porous carrier is contacted with saidliquid in step (i) in the absence of ball milling.
 41. A processaccording to claim 40, wherein R and R' are unsubstituted C₁ -C₁₂ alkylsand n is
 1. 42. A process according to claim 41, wherein said contactingstep (i) comprises:(a) slurrying said carrier in a non-Lewis baseliquid; and (b) adding said organomagnesium composition to said slurryof step (a) in the form of an ether solution of said organomagnesiumcomposition.
 43. A process according to claim 42, wherein said solid,porous carrier is substantially composed of silica, alumina orcombinations thereof.
 44. A process according to claim 43, wherein saidsolid, porous carrier is silica having from about 0.3 to about 0.7mmoles/gram of said OH groups.
 45. A process according to claim 44wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 1.1 to about 2.5.
 46. A process according toclaim 45 wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 1.5 to about 2.5.
 47. A process according toclaim 46, wherein, in step (i), the ratio of the number of moles of saidorganomagnesium composition to the number of moles of said OH groups onsaid silica is from about 2.0 to about 2.5.
 48. A catalyst compositionfor use in alpha-olefin polymerization reactions, prepared by a processconsisting essentially of the steps of:(i) contacting, in the absence ofan organoaluminum or aluminum halide compound, a solid, porous carrierhaving reactive OH groups with a liquid, said liquid containing at leastone organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different C₁ -C₁₂ hydrocarbyl groups andn is a rational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to obtain a carrier, containing magnesium, in theform of a dry, free-flowing powder; and (iii) reacting said powder ofstep (ii) with at least one transition metal compound in a liquidmedium, the number of moles of said transition metal compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said transition metal compound being soluble in said liquid medium,and said magnesium of said carrier being substantially insoluble in saidliquid medium, whereby a reacted form of transition metal which isinsoluble in said liquid medium becomes supported on said carrier.
 49. Acatalyst composition of claim 48 wherein said solid, porous carrier iscontacted with said liquid in step (i) in the absence of ball milling.50. A catalyst composition of claim 49 wherein R and R' areunsubstituted C₁ -C₁₂ alkyls and n is
 1. 51. A catalyst composition ofclaim 50, wherein said contacting step (i) comprises:(a) slurrying saidcarrier in a non-Lewis base liquid; and (b) adding said organomagnesiumcomposition to said slurry of step (a) in the form of an ether solutionof said organomagnesium composition.
 52. A catalyst composition of claim51, wherein said solid, porous carrier is substantially composed ofsilica, alumina or combinations thereof.
 53. A catalyst composition ofclaim 52 wherein said solid porous carrier is silica having from about0.3 to about 0.7 mmoles/gram of said OH groups.
 54. A catalystcomposition of claim 53 wherein, in step (i), the ratio of the number ofmoles of said organomagnesium composition to the number of moles of saidOH groups on said silica is from about 1.1 to about 2.5.
 55. A catalystcomposition of claim 54 wherein, in step (i), the ratio of the number ofmoles of said organomagnesium composition to the number of moles of saidOH groups on said silica is from about 1.5 to about 2.5.
 56. A catalystcomposition of claim 55, wherein, in step (i), the ratio of the numberof moles of said organomagnesium composition to the number of moles ofsaid OH groups on said silica is from about 2.0 to about 2.5.
 57. Acomposition of matter prepared by a process consisting essentially ofthe steps of:(i) contacting, in the absence of an organoaluminum oraluminum halide compound, a solid, porous carrier having reactive OHgroups with a liquid, said liquid containing at least oneorganomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different C₁ -C₁₂ hydrocarbyl groups, andn is a rational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; and (ii) evaporatingsaid liquid from step (i) to obtain a carrier, containing magnesium, inthe form of a dry, free-flowing powder.
 58. A composition of claim 57,wherein said solid, porous carrier is contacted with said liquid in step(i) in the absence of ball milling.
 59. A composition of claim 58,wherein R and R' are unsubstituted C₁ -C₁₂ alkyls and n is
 1. 60. Acomposition of claim 59, wherein said contacting step (i) comprises:(a)slurrying said carrier in a non-Lewis base liquid; and (b) adding saidorganomagnesium composition to said slurry of step (a) in the form of anether solution of said organomagnesium composition.
 61. A composition ofclaim 60, wherein said solid, porous carrier is silica, alumina orcombinations thereof.
 62. A composition of claim 62, wherein said solidporous carrier is silica having from about 0.3 to about 0.7 mmoles/gramsof said OH groups.
 63. A composition of claim 63, wherein, in step (i),the ratio of the number of moles of said organomagnesium composition tothe number of moles of said OH groups on said silica is from about 1.1to about 2.5.
 64. A composition of claim 63, wherein, in step (i), theratio of the number of moles of said organomagnesium composition to thenumber of moles of said OH groups on said silica is from about 1.5 toabout 2.5.
 65. A composition of claim 64, wherein, in step (i), theratio of the number of moles of said organomagnesium composition to thenumber of moles of said OH groups on said silica is from about 2.0 toabout 2.5.
 66. A composition of claim 65, wherein chemically andphysically bound water has been removed from said silica in step (i) byheating at a temperature from about 750° C. to about 850° C. for atleast four hours, and the organomagnesium composition of formula (I) isC₂ H₅ MgCl.
 67. A process for preparing a supported catalyst compositionfor use in alpha-olefin polymerization reactions, said processconsisting essentially of the steps of:(i) contacting, in the absence ofan organoaluminum or aluminum halide compound, a solid, porous carrierhaving reactive OH groups with a liquid in the absence of ball milling,said liquid containing at least one organomagnesium composition havingthe empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different C₁ -C₁₂ hydrocarbyl groups andn is a rational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to precipitate magnesium onto said carrier, saidprecipitated magnesium being selected from the group consisting ofmagnesium dihalide, unreacted organomagnesium and mixtures thereof,whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and (iii) reacting said powder of step(ii) with at least one tetravalent titanium compound in a liquid medium,the number of moles of said tetravalent titanium compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said tetravalent titanium compound being soluble in said liquidmedium, and said supported magnesium composition being substantiallyinsoluble in said liquid medium, whereby a reacted form of titaniumwhich is insoluble in said liquid medium becomes supported on saidcarrier.
 68. A process according to claim 67, wherein R and R' areunsubstituted C₁ -C₁₂ alkyls and n is
 1. 69. A process according toclaim 68, wherein said contacting step (i) comprises:(a) slurrying saidcarrier in a non-Lewis base liquid; and (b) adding said organomagnesiumcomposition to said slurry of step (a) in the form of an ether solutionof said organomagnesium composition.
 70. A process according to claim69, wherein said solid, porous carrier is substantially composed ofsilica, alumina or combinations thereof.
 71. A process according toclaim 70, wherein said tetravelent titanium compound is TiCl₄.
 72. Asupported catalyst composition for use in alpha-olefin polymerizationreactions, prepared by a process consisting essentially of the stepsof:(i) contacting, in the absence of an organoaluminum or aluminumhalide compound, a solid, porous carrier having reactive OH groups witha liquid in the absence of ball milling, said liquid containing at leastone organomagnesium composition having the empirical formula

    R.sub.n MgR'.sub.(2-n)                                     (I)

where R and R' are the same or different C₁ -C₁₂ hydrocarbyl groups, andn is a rational number from about 0.5 to 2, the number of moles of saidorganomagnesium composition being in excess of the number of moles ofsaid OH groups on said carrier, whereby said organomagnesium compositionis reacted with said OH groups on said carrier; (ii) evaporating saidliquid from step (i) to precipitate magnesium onto said carrier, saidprecipitated magnesium being selected from the group consisting ofmagnesium dihalide, unreacted organomagnesium and mixtures thereof,whereby a supported magnesium composition in the form of a dry,free-flowing powder is formed; and (iii) reacting said powder of step(ii) with at least one tetravalent titanium compound in a liquid medium,the number of moles of said tetravalent titanium compound being inexcess of the number of said OH groups on said carrier prior to thereaction of said carrier with said organomagnesium composition in step(i), said tetravalent titanium compound being soluble in said liquidmedium, and said supported magnesium composition being substantiallyinsoluble in said liquid medium, whereby a reacted form of titaniumwhich is insoluble in said liquid medium becomes supported on saidcarrier.
 73. A supported catalyst composition of claim 72 wherein R andR' are unsubstituted C₁ -C₁₂ alkyls and n is
 1. 74. A supported catalystcomposition of claim 73, wherein, in step (i), the ratio of the numberof moles of said organomagnesium composition to the number of moles ofsaid OH groups on said silica is from about 1.1 to about 2.5.
 75. Asupported catalyst composition of claim 74 wherein, in step (i), theratio of the number of moles of said organomagnesium composition to thenumber of moles of said OH groups on said silica is from about 1.5 toabout 2.5.
 76. A supported catalyst composition of claim 75 wherein, instep (i), the ratio of the number of moles of said organomagnesiumcomposition to the number of moles of said OH groups on said silica isfrom about 2.0 to about 2.5.